Process for production of nu-alpha-olefins by the alkyl metal technique



Nov. 14, 1967 m 5:3515 mzmnpm o M L I um m E MN5 f m f f N N C l m MF m. NMMM m, UO T 4 Eu L w v om mm 1.56m@ P Ai O- wmp .F T N Rs n m 3 2:2 vo fw. 53 tm m 5.5050: so.. mlm wzmd I N VEN TORS Joseph Serrorore United States Patent Oiice 3,352,940 Patented Nov. 14, 1967 This invention relates to the preparation of normal alpha oleiins. More particularly, this invention pertains to a novel process for the synthesis of a full range of straight chain alpha olens by a process which involves the growth of la low molecular weight talkene onto a low molecular weight aluminum alkyl so las to a produce a range of aluminum alkyls having a narrowed Poisson distribution of the desired C12-C20 alkyl chain lengths and subsequently the olens produced therefrom.

It is known in the prior art to prepare a full range of C6 through C20 normal oleiins by a yprocess comprising the steps of: (l) adding or growing ethylene onto low molecular weight, i.e. C2-C6, aluminum trialkyls to produce higher molecular weight -aluminum tIialkyls, (2) reacting said growth higher aluminum trialkyls with low molecular weight oleiins to obtain a displacement of the higher molecular weight alkyl groups by said lower oleiins thus forming higher olefins and lower molecular weight aluminum trialkyls corresponding to the displacing oletins, and (3) separating the displaced higher molecular weight olens as product from the lower molecular weight aluminum alkyls formed in the displacement reaction, which lower alkyls are recycled to the process.

To further illustrate the above general type of reaction with which this invention is concerned, reference may be had to the 4following equations, with (1) representing the reaction of aluminum triethyl with ethylene to form higher molecular weight aluminum alkyls having a molecular weight distribution such as described in Table I. Reaction (2) sets forth a displacement Ireaction wherein a lower molecular weight olelin, such as n-butylene, is reacted with the aluminum alkyl growth product at moderately elevated temperatures and, if desired, in the presence of a catalyst to cause displacement of the alkyl side chains by the butylene, thus generating normal olens corresponding to the alkyl chains displaced.

However, the prior art pro-cessess employing the above general type of reaction have been limited to the production of a mixture of olens in which there is a predominance of the CS-Clo and lower oleins, since the mixture obtained has a Poisson distribution of the various carbon numbers. For example, the preparation lof n--oleiins via the above-mentioned AM (alkyl metal) technique will yield a random distribution of n--oleiins following the Poisson equation:

where n is the average ethylene absorbed by the starting alkyl and p is the number 4of ethylene units in a given homologue. Thus, when ethylene is reacted with or grown onto aluminum triethyl under elevated temperatures and pressures, the resultant product contains a mixture of aluminum trialkyls wherein the alkyl chains contain a range of from 4 to 24 carbon atoms, :but mainly 4 to lo carbon atoms and especially 6 to 10 carbon atoms. A typical product from such :a reaction comprises the follow distribution:

TABLE I Composition of growth The above alkyls will generally be present in aluminum compounds of heterogeneous composition; that is, a single aluminum trialkyl molecule may and usually does contain alkyl groups of diiierent chain lengths. In any even, it will be noted that an inherent disadvantage is that the growth product normally comprises substantially lower amounts of C12-C20 and :higher alkyl radicals than the C65-C10 and lower alkyl radicals. The olens obtained from the C12- C20 or higher alkyl aluminum compounds are extremely valuable since they are useful as intermediates for various reactions including the synthesis of detergent alkyla-te, alcohols, acids and the like. These intermediates are particularly desirable since the end products will be of the straight chain variety. Thus, for example the C12-C20 or higher olens are an excellent feed stock for detergent alkylate manufacture.

Another disadvantage of the prior art process is that such processes have also been limited generally to the production of Ca-Cw oleiins .because no practical methods were known for completely separating `oleiins boiling higher than about C10 or at most C12 oleiins from the aluminum alkyls remaining after the displacement reaction inasmuch as the higher boiling C12 and higher olens could not be distilled overhead from the liquid aluminum alkyls due to the relatively low decomposition temperatures of said aluminum alkyls and/or the closely similar boiling ranges of the lower aluminum alkyls and these higher oleins. Thus, according to the prior art processes, it was usually necessary to closely regulate the growth conditions so as to obtain a minimum rather than a maximum amount of C12 and higher oletins. Additionally, those higher oleiins which were formed required removal by purging, which involved the loss of an important amount of commingled, valuable aluminum alkyls. Further, in order to keep these aluminum alkyl purge losses to a minimum, it was necessary in the prior art process to allow the C12 Iand higher olefin content of the recycle aluminum alkyl stream to build up to fairly high levels, which falso deleteriously affected the process due to the cost of circulating large amounts of this material.

Further, while olefins, eg., C12 and higher olefins, which may be recycled to the growth reactor with the recycle aluminum alkyl stream do react to some extent with growth product to ultimately form higher olefms, such resulting olefins are highly branched in structure. This branching effect is shown in the following Table II which shows the branched olen content without use of olefin recycle to the growth reactor as compared with the recycle of higher olefins with recycle aluminum triethyl:

TAB LE II Percent Branched Olens Olctin With Recycle Without Recycle C 1S I6 5 C 20 8 C22 25 I() It is, therefore, an object of this invention to provide an improved method for the selective production of highly valuable C12-C20 and higher olefins from aluminum alkyls and ethylene.

It is a further yobject of this inventionto provide an improved continuous cyclic method for the selective production of substantially unbranched C12-C20 and higher olefins from aluminum alkyls and ethylene.

It is a further object of this invention to narrow the Poisson distribution and thereby produce in a continuous manner, by the growth process, an aluminum alkyl product having a `predominance of C12-C20 and higher alkyl radicals.

Itrshould be here noted, with reference to the description of the aluminum trialkyls throughout the specification and claims, that the number of carbon atoms described (eg. C4) refers to the number in each alkyl group.

According to the present invention, it has now been discovered that preparation of predominantly straight chain C12-C20 olefins can be effected by a process for the preparation of said olefins which comprises continuously feeding C2-C3 olefins, preferably ethylene, and a lower molecular weight aluminum trialkyl into a growth reaction zone at elevated temperatures and pressures, reacting in said zone said CZ-CS olefins and lower molecular weight aluminum trialkyl, and recovering from said zone an aluminum trialkyl growth product. The improvement of the present invention comprises separating said growth product into a lower molecular weight aluminum trialkyl fraction and a higher molecular weight aluminum trialkyl fraction, subjecting said lower molecular weight aluminum trialkyl fraction to further growth in a growth reaction zone and passing said higher molecular weight aluminum trialkyl fraction to a displacement zone.

The present invention will be more clearly understood from a consideration of the accompanying drawing, which presents a prefe-rred processing scheme for carrying out the present invention. Turning now to the drawing, a C2-C3 olefin feed, in this instance, an ethylene stream containing small amounts of ethane (eg. up to about 2 mol percent) is passed from line 1 and line 3 to growth lreactor 4. Lower molecular weight aluminum trialkyl is supplied from line 2 and line 3 to growth reactor 4. Suitable aluminum trialkyls, that is compounds having the formula:

wherein R1, R2, and R3 .may represent similar or different alkyls, include compounds wherein the alkyl group contains from 2 to 8 carbon atoms. Thus aluminum triethyl, aluminum tripropyl, aluminum tributyl, aluminum tripentylare suitable for use in the instant invention. Aluminum triethyl is especially preferred. In the growth reactor 4 under appropriate reaction conditions ethylene is grown onto the aluminum trialkyls until the trialkyls contain an increased number of carbon atoms, for example, from 4 to 20 and higher. Growth conditions in the processes of this `invention may be as follows:

Temperature, 16C-350, preferably 20C-300, specifically Pressure, SOO-500() p.s.i.a., preferably 1000-3000, specifically l600 p.s.i.a.

Reaction times, 0.2-10 hours, preferably 0.6-5 hours, specifically 2 hours.

Mols of ethylene permol of starting aluminum alkyl, 0.5-

20, preferably 2-14, specifically 5.

Following the growth stage, the effluent is passed from reactor 4 through line 5 to separator 6. Here, in accordance with the instant invention, lower molecular weight aluminum trialkyls are separated overhead and are recycled -to the process through line 7. The lower molecular weight aluminum trialkyl fraction separated comprises a mixture containing a predominance of C2, C4, C6 and C8 alkyl groups. Some alkyl groups with more carbon atoms will also be ypresent in the separated fraction, although usually in small to negligible amounts. For example, the distillation of the Growth alkyl illustrated in Table I would result in the distillate composition `set forth in the following Table III. In addition to such distillate composition, Table III also illustrates the percent of each Growth alkyl component of Table I distilled overhead.

TABLE IIL-DISTILLATION OF "GROWTH" ALKYL OF TABLE I A preferred method of separating the lower molecular weight aluminum trialkyl fractions is by distillation of the growth alkyl product using a short residence time evaporator or by a molecular distillation technique.r Operating conditions may be as follows:

Temperature, -600, preferably 370-500 F., specifically 480 F.

Pressure, 10-6-10 mm., preferably 104l mm., specifically 0.1 mm.

Residence time, 0.01-10 seconds, `preferably y.12 sec.,

specifically 1 second.

It should be noted that it is considered within thescope of the present invention to carry out the subsequent growth of the distillate from the above-mentioned distillation in a reactor other than the primary growth reactor referred to above. Thus, the distillate may be passed directly to a second and different growth reactor rather than be recycled to the primary growth reactor.

The overhead product is recycled to the reactor for further buildup, thus increasing the ultimate yield of desired C12-C21, olefins based on ethylene consumed `and narrowing the Poisson distribution of the final equilibrium product.

The higher molecular weight aluminum trialkyls comprising a predominance of C10 and higher, for example up to C24, aluminum trialkyls are taken as bottoms from separator 6 through line 8 to displacement with a higher molecular weight alpha olefin to yield the C10-C24 n. alpha olefin and the corresponding higher aluminum trialkyl. If desired, the liquid phase from separator 6 is passed through line 8 to a further separator (not shown) where at reduced pressure, a purge stream containing ethane is passed from the process. The degassed liquid aluminum alkyls are then passed through line 9 to displacement reactor 10 wherein the growth stage aluminum alkyl product is contacted with higher alpha olefin supplied thro-ugh line 11. This displacement and the other displacement reactions of this invention may be conducted in the presence of a suitable catalyst such as a nickel or cobalt, preferably nickel catalyst, or without a catalyst. Suitable catalysts are liquid materials such as nickel acetyl acetonate, or colloidal nickel, solid materials such as Raney nickel, and supported materials such as nickel sulfide or alumina. The type of catalyst used generally is not important, however, it is preferred to utilize a catalyst in liquid phase operations and not to use one in Vapor phase operations. In liquid phase operations using nickel acetyl acetonate or colloidal nickel as the catalyst the amount of catalyst used may be for example 0.2-0.5 mole percent based on alkyls, specifically, 0.3 mole percent. These equilibrium displacement reactions should be carried out at conditions which minimize double bond migration and skeletal isomerization of the product olefins. Temperature, and to a lesser degree, time, are most important in this respect. At the same time yield considerations necessitate practical minimums for these variables. Of course, the law of mass action can be effectively employed by utilizing a large excess of displacing olefin or by running the displacement reaction in vapor phase with respect to the displacing olefin thereby to cause said olefin to substantially remove the olefins displaced as formed. The conditions in the displacement reactors, which vmay be run in either liquid or gas phase with respect to the displaced olefins, may vary to considerable extent, being determined for any particular embodiment by the characteristics of the reactants and the equipment available. However, generally at least 3 moles of displacing olefins per mole of C8 and higher aluminum alkyls are utilized with preferably l to 100 or more moles/mole, and specifically 50 moles being employed.

The product from the displacement step is passed from the reactor through line 12 to recycle olefin tower 13. In said tower unreacted excess alpha olefin is separated overhead under a vacuum suficient to prevent a thermal decomposition of the aluminum alkyl containing bottoms at the distillation temperature. Thus, tower 13 is operated at preferably mm. to 760 mm. Hg overhead pressure and a ltemperature of from 70 to 275 F. The alpha olefin stream is passed overhead through line 11 and recycled through said line 11 to the displacement reactor 10.

From the bottom of tower 13 the displaced product olens and higher aluminum trialkyls are passed through line 14 to tower 15. Here C8 to C16 olefins are separated overhead through line 16. Tower 15 is operated at an overhead pressure suciently reduced, i.e. preferably around .01 to l0 mm. Hg, to limit or prevent thermal decomposition of the aluminum trialkyl containing bottoms, which trialkyls decompose at about 230 to 270 F. Thus, an eliicient separation is obtained of a substantial part of the C16 olefin (boiling at 260 F.) at 5 mm. Hg and all of the C14 and lighter material (boilingat 220 F.) from the higher aluminum trialkyl plus C1B and higher olefin bottoms.

From the bottom of tower 15 the higher aluminum trialkyl along with the higher boiling olefins are passed through line 17. At least part of the stream is passed to a secondary displacement reactor. Here ethylene is supplied with the result that the higher alkyl chains are displaced with ethylene thus forming aluminum triethyl and higher alpha olefins. The aluminum triethyl is recycled to the growth reactor and the relatively pure olefins are passed to conventional purification or may be used as such.

It is, of course, also contemplated according to this invention that alternatively the initial displacement reaction may be run using a different displacing olefin to obtain the corresponding aluminum trialkyl or employ any other conventional modification to effect the desired displacement.

It should be noted here that the necessity for a purge stream is entirely eliminated in the present invention process. This is extremely important in that, although in the prior art processes the olefins mixed with the aluminum alkyls in the purge stream can be recovered by hydrolysis, the much more valuable aluminum trialkyls were destroyed in the hydrolysis. It should be noted that in both the prior art processes and the present invention process the valuable aluminum alkyls for the most part (except for any purge or other losses) are not consumed but rather are merely continuously recycled in the process. Thus, by the present invention, for the first time essentially complete recovery and recycle of aluminum alkyls is obtained thus greatly reducing the total cost of the product olefins produced. This is true regardless of whether C12-C20 or higher range of olefins is desired or whether, as in prior art processes, production of C8-C10 olefins is preferred. In any event, growth conditions may now be controlled to obtain exactly the product distribution desired rather than unnecessarily recycling higher aluminum alkyls as was formerly required.

In summary, it should be noted that according to the process of the present invention:

(l) Higher, C10+ olefins can now be produced in predominance due to narrowed Poisson distribution.

(2) Purging of valuable trialkyls is eliminated.

(3) Growth step limitations are removed so that the growth step can be operated to give the desired C10-C20 product distribution at the economic optimum.

To set forth a specific operative embodiment of this process, the following examples are submitted showing specific and general conditions which enable one skilled in the art to operate a process such as described above and claimed hereinafter.

Example I This example illustrates the conditions employed in the distillation of the growth alkyl product from a growth reactor as hereinbefore described and, in addition, illustrates the distribution of the components of the growth product before distillation as well as the distribution in the distillate and bottoms recovered after distillation.

Three distillation experiments, using a C average growth alkyl product as feed, were carried out at Various feed rates using an Asco 50.2 Rotafilm molecular still. The molecular stills in each of the runs, referred to as Run A, Run B and Run C were operated under the following conditions:

1 Hydrolysis.

hylene units as Bottoms Run C, Recovery in Overhead osition of the distillation feed and products itions for both Examples 2 and 3 are f narrowing the Poisson Initial A1B; Product, R=C5 Example 2 Example 3 Avg. Alkyl of an AlRa with C4 average R groups and the blended composition is grown by two average et compared to one in Example 2.

Bottoms The comp at equilibrium cond Oletln Fraction, Mole Percent tabulated in Table V. The extent o distribution to a higher yield of C12-C20 n-a-olens is outlined in the following summarized table Run B, Recovery in- Overhead product fed to the f the resulting pro Bottoms duced by the use lustrated in Table I.

containing C8 l to distillation. The

growth Run A, Recovery in- Overhead illustrate that higher yields e 2 illustrates the use h a C8 average chain before il lined in the following recovered in the overhead forth in the table. This distil-` The composition of the molecular still and the composition o ucts are given in weight percent:

Growth" Composition Product Feed to Still Examples 2 and 3 The following two examples of the desired n-u-olefins can be pro in accordance with the practice` trialkyl product wit inum triallcyl` (AIRS) of distilled growth alkyls of the present invention. Exampl of a growth length similar to that herein The procedure employed is out Table IV. An alum average R groups was taken as feed percent of each component fraction from the feed is set C2-C1o.

s X in the Addition olv lst Dlstillote Recycle to Point x Recycle at Point x in Growth Reactor, Mole Percent Composition at Point x l ile maintaining a high yield Distillate Composition in Mole Percent of Total Feed Lof/.362100. 1l1

3. This increase of 30.05 mole percent can be recess where only small amounts of C227L .alkyl rhead MOLECULAR WEIGHT ALUMINUM TRIALKYLS BACK GROWTH REACTOR Distillation of Growth Percent of Each Cornponent in Ove Thus, the original Poisson distribution for a C8 average aluminum trialkyl has been altered in the C12-C20 range his from 18.99 to 49.14 mole percent when comparing 1t t0 Example utilized in a p material can be tolerated wh of C2`-C20 n-a-olens.

To THE Composition of Growth Alkyl Feed, in Mole Percent average R groups. T

o an average of one ethle and growth is repeated TABLE 1v late is recycled to a point referred to a growth reactor which at that point conta position of an AlR3 with C6 blended composition is grown t ylene unit. The distillation, recyc until equilibrium conditions are reache tions, it is determined that t Example 3 is similar to Example 2 except t cycle stream growth reactor which at that point contains a composition l Point x composition was taken as au AKCHi; avgJe calculated from the Poisson equation.

TABLE V.-EQUILIBRIUM COMPOSITION OF AlRa FEED A PRODUCTS OBTAINED FROM FEE NDD OF DISTILLATION Distillation of AlR3 Feed AlRa Feed Components, Mole Distillate Residue Percent Example 2 Example 3 Example 2 Example 3 Example 2 Example 3 Al(C2H4)3 2.26 1.89 2. 26 1.89 l1. 47 9. 69 9. 03 7. 64 2. 44 2. 05 21. 35 17. 75 16. 2 13. 45 5. 15 4. 30 24. 23 20. 99 14. 6 12. 64 9. 63 8. 35 19. 36 18. 97 6. 93 6. 79 12. 43 12. 18 11. 84 13. 92 2. 27 2. 67 9. 57 11. 25 .Al(C14H20)3 5. 83 8. 61 0- 62 0- 9]. 5. 2l. 7.70 AKCmHggh 2. 4l 4. 62 0.12 0. 23 2. 29 4. 39 A1(C1sHs7)3. 0. 86 2. 16 0. 86 2. 16 A1( C20H41)3 0. 27 0. 91 0.27 0. 91 Al(C2zH4a)a 0. 07 0. 33 0. 07 0. 33 AKCMHMJ. 0. 02 0. 09 0. 02 0. 09 Al(C2sH53)z O. 03 0. 03 Al( CRI-15703 0. 01 0. 0l

Example 4 dominance of CZ-C8 aluminum trialkyl and a h1gher The procedure of this example is similar to Examples 2 and 3 with the exception that the A1113 used is a C12 average R group instead of a C8 average R group. The equilibrium composition that is obtained after three recycles of distillate is set forth in the following tabulation which compares the Poisson distribution of aluminum trialkyls with C12 average R groups to that of the equilibrium product after distillation and recycle.

Initial AlRs Olefiu Fraction Product Where Example 4 R C12 Avg. Allryl Mole percent 43. 52 23. 99

Wt. percent 29.01 16.05 U12-h2o.

Mole percent... 52. 79 71. 53

Wt. percent 63. 44 76. 57

Mole percent 3. 69 4. 48 Wt. percent 7. 55 7. 87

Example 4 illustrates a definite improvement over the growth product having C12 average alkyl chain lengths as the C12-C20 range increased 13.13 weight percent.

What is claimed is:

1. In a process for the preparation of normal alpha oleflns which comprises feeding a C2-C3 olefin and a lower molecular weight aluminum trialkyl wherein each of said alkyls contains from 2 to 6 carbons atoms into a growth reaction zone at elevated temperatures and pressures, reacting in said zone said C2-C3 olefin and lower molecular weight aluminum trialkyl, and recovering from said zone an aluminum trialkyl growth product, the improvement which comprises separating said growth product into a lower molecular weight aluminum trialkyl fraction comprising a predominance of CZ-C aluminum trialkyls and a higher molecular weight aluminum trialkyl fraction comprising a predominance of C10, and higher, aluminum trialkyls, subjecting said lower molecular weight aluminum trialkyl fraction to further growth in a growth reaction zone and passing said higher molecular weight aluminum trialkyl fraction to a displacement zone.

2. In a process for the preparation of normal alpha olelins which comprises feeding a C2-C3 olefin and a lower molecular weight aluminum trialkyl wherein each of said alkyls contains from 2 to 6 carbon atoms into a growth reaction zone at elevated temperatures and pressures, reacting in said zone said C2-C3 oleiin and lower molecular weight aluminum trialkyl, and recovering from said zone an aluminum trialkyl growth product, the improvement which comprises distilling said growth product at a temperature of from about 100 to about 600 F., under a pressure of 10-6 to 10 mm. of Hg and for a residence time of from about 0.01 to 10 seconds so as to produce a lower molecular weight distillate comprising a premolecular weight fraction comprising a predominance of C10-C14 aluminum trialkyls, subjecting said lower molecular weight distillate to further growth in a growth reaction zone and passing said higher molecular weight fraction to a displacement Zone.

3. A continuous cyclic process for the selective production of straight chain C12-C20 olelins which comprises feeding ethylene and a lower molecular weight aluminum trialkyl wherein each of said alkyls contain from 2 to 6 carbon atoms into a growth reaction zone at elevated temperatures and pressures, reacting in said zone said ethylene and lower molecular weight aluminum trialkyl, recovering from said zone an aluminum trialkyl growth f product, separating said growth product into a lower molecular weight aluminum trialkyl fraction comprising a predominance of C2C3 aluminum trialkyls and a higher molecular weight aluminum trialkyl fraction comprising a predominance of C10, and higher, aluminum trialkyls, recycling said lower molecular weight aluminum trialkyl fraction to said growth reaction zone and passing said higher molecular weight aluminum trialkyl fraction to a displacement zone.

4. The process of claim 3 in which said lower molecular weight aluminum trialkyl fraction is separated from the higher molecular weight aluminum trialkyl fraction by distillation of the growth alkyl product at a temperature of from about to about 600 F., under a pressure of 10-6 to 10 mm. of Hg and for a resid-ence time of from about 0.01 to 10 seconds.

5. A continuous cyclic process for the preparation of an oleiin product having a predominance of straight chain C12-C20 oleiins which comprises reacting ethylene with a C2-C6 aluminum alkyl in a reaction zone at a temperature of from to 300 F. and a pressure of from 500 to 5000 p.s.i.a. to produce a growth product comprising higher molecular weight aluminum alkyls containing from 4 to 20 and more carbon atoms, recovering said growth product from said reaction zone, distilling from said growth product a lower molecular weight aluminum trialkyl fraction containing predominantly C2-C8 alkyls, said distillation being carried out at a temperature of from about 370 to about 500 F., under a pressure of 101 to l mm. of Hg and to a residence time of 0.1 to 2 seconds, recycling said lower molecular weight aluminum trialkyl fraction to said growth reaction zone, and passing at least a portion of the remainder of the growth product to a displacement zone.

References Cited PAUL M. COUGHLAN, JR., Primary Examiner. 

1. IN A PROCESS FOR THE PREPARATION OF NORMAL ALPHA OLEFINS WHICH COMPRISES FEEDING A C-2C-3 OLEFIN AND A LOWER MOLECULAR WEIGHT ALUMINUM TRIALKY WHEREIN EACH OF SAID ALKYLS CONTAINS FROM 2 TO 6 CARBONS ATOMS INTO A GROWTH REACTION ZONE AT ELEVATED TEMPERATURES AND PRESSURES, REACTING IN SAID ZONE SAID C2-C3 OLEFIN AND LOWER MOLECULAR WEIGHT ALUMINUM TRIALKYL, AND RECOVERING FROM SAID ZONE AN ALUMINUM TRIALKYL GROWTH PRODUCT, THE IMPROVEMENT WHICH COMPRISES SEPARATING SAID GROWTH PROD- 